钌（Ⅱ）配合物[Ru（btz）3]2＋和[Ru（btz）（dppz）2]2＋的合成、DNA键合及光断裂研究

本文设计合成了两个含有联噻唑的钌（Ⅱ）配合物[Ru（btz）3]（CIO4）2（1）和[Ru（btz）（dppz）2]（c104）2（2）（btz=4,4’bithiazole,dppz：dipyrido[3,2-a：2’,3’c]phenazine）．通过元素分析、ES-MS、1HNMR和X射线单晶衍射表征了配合物的结构．运用光谱滴定和黏度实验研究了配合物与DNA的作用,发现配合物1与DNA以静电方式结合,配合物2以插入模式与DNA结合．凝胶电泳实验表明配合物1和2在光照射下均可有效断裂DNA,单线杰氢（1O2）和脊某自由墓（OH、县推动断裂反应的活性物种．     

配体的空间构型及疏水性对钌（Ⅱ）多吡啶配合物与DNA作用的影响

合成了4－氰基苯基咪唑并[5,6-f]邻菲咯啉（CYIP）和2－羧基苯基咪唑并[5, 6-f]邻菲咯啉（COIP）两种新配体及它们的钌混配配合物[Ru(bpy)2CYIP](ClO4)2 ·H2O（Rul）（bpy=2,2′-联吡啶），[Ru(phen)2CYIP](ClO4)2·H2O(Ru2) (phen=1,10-邻菲咯啉），[Ru(bpy)2COIP](ClO4)2·3H2O(Ru3)和[Ru(phen)2COIP] (ClO4)2·H2O(Ru4)，并用红外光谱、紫外光谱、核磁和质谱对它们进行了表征。 通过循环伏安法研究了这些配合物的电化学性质。采用电子吸收光谱、稳态荧光、 圆二色谱和粘度测定研究了配合物与小牛胸腺DNA的相互作用。结果表明配合物 Rul和Ru2通过CYIP配体以插入的方式与DNA结合，而配合物Ru3和Ru4则通过COIP配 体以部分插入的方式与DNA结合。     

钌(II)多吡啶配合物的合成、荧光性质及与脱氧核糖核酸DNA的 作用机制研究

设计合成含多个配位中心的多吡啶配体ODCIP (3,4-二氯基苯并咪唑并[4,5-f][1,10]邻菲咯啉)及其钌(II)多吡啶配合物[Ru(bpy)2ODCIP]2＋. 运用元素分析、红外光谱、核磁谱和质谱对配体及配合物进行结构表征. 利用紫外吸收光谱、荧光光谱和粘度法研究了[Ru(bpy)2ODCIP]2＋与DNA(脱氧核糖核酸)的作用机制、与Co2＋配位后与DNA的作用机制及其荧光变化情况. 结果表明[Ru(bpy)2ODCIP]2＋与DNA通过部分插入模式作用, [Ru(bpy)2ODCIP]2＋与Co2＋配位形成的双核配合物[Ru(bpy)2(ODCIP)Co]4＋也能与DNA插入结合. 进一步利用稳态荧光发射光谱、荧光淬灭实验等方法研究了单核配合物[Ru(bpy)2ODCIP]2＋和双核配合物[Ru(bpy)2(ODCIP)Co]4＋的荧光性质.     

金属四重键化合物M2X4（PMe3）4（M=Cr，Mo，W;X=F，CI，Br，I）结构和电子光谱的密度泛函理论研究

采用密度泛函理论方法，在TZ2P-STO基组水平下，对金属四重键化合物M2Cl4（PMe3）4（M=Cr，Mo，W）和Mo2X4（PMe3）4（X=F，Cl，Br，I）的几何结构进行优化，分析了电子结构，并运用TDDFT方法对其低占据激发态进行了计算．考虑相对论效应的ZORA方法能够较好地重现M2X4（PMe3）4的几何结构．M2X4（PMe3）4的电子结构分析表明其d电子的组态为σ^2π^4δ^2，前线轨道能级顺序为πlig〈πd／σd〈δd〈δd^＊．金属原子和卤素配体的改变虽然使轨道能量发生变化，但没有影响轨道的排布顺序．TDDFT方法对M2Xa（PMe3）4δd→δd^＊和π→δd^＊跃迁能量的计算较为准确，对πlig→δd^＊（LMCT）跃迁能量的计算误差较大．金属原子、卤素配体以及相对论效应对激发能的影响可以根据分子轨道能级的变化给予解释．     

DFT法研究阴离子识别剂[Ru（bpy）2L]2+（L=H2biim,H2bbim）去质子后结构变化

配合物[Ru(bpy)2(H2biim)](PF6)2(1)(bpy=2,2′-联吡啶,H2biim=2,2′-联咪唑)和[Ru(bpy)2(H2bbim)](PF6)2(4)(H2bbim=2,2′-苯并联咪唑)是良好的阴离子识别剂.用密度泛函理论方法研究了2种阴离子识别剂脱去质子后的几何结构和电子结构的变化.计算结果表明:脱去质子后配合物HOMO轨道上电子云分布由中心钌原子转移到(苯并)联咪唑上,而LUMO轨道虽然能量增加但电子云仍然分布在bpy配体上;另外,最高占居轨道HOMO与最低空轨道LUMO的能量差ΔεL-H逐渐减小,相对于配合物的吸收波长增大,所以分子的吸收峰发生红移,这与实验现象相吻合。     

钌（Ⅱ）多吡啶配合物的合成、荧光性质及与脱氧核糖核酸DNA的作用机制研究

设计合成含多个配位中心的多吡啶配体ODCIP(3,4-二氯基苯并咪唑并[4,5-f][1,10]邻菲咯啉)及其钌(Ⅱ)多吡啶配合物[Ru(bpy)2ODCIP]2 .运用元素分析、红外光谱、核磁谱和质谱对配体及配合物进行结构表征.利用紫外吸收光谱、荧光光谱和粘度法研究了[Ru(bpy)2ODCIP]2 与DNA(脱氧核糖核酸)的作用机制、与Co2 配位后与DNA的作用机制及其荧光变化情况.结果表明[Ru(bpy)2ODCIP]2 与DNA通过部分插入模式作用,[Ru(bpy)2ODCIP]2 与Co2 配位形成的双核配合物[Ru(bpy)2(ODCIP)Co]4 也能与DNA插入结合.进一步利用稳态荧光发射光谱、荧光淬灭实验等方法研究了单核配合物[Ru(bpy)2ODCIP]2 和双核配合物[Ru(bpy)2(ODCIP)Co]4 的荧光性质.     

[NiCl（Ph2PCH2CH2OH）2Cl·H2O]^＋Cl^-和[Ni（Ph2P（O）CH2CH2OH）4]^2＋[NiCl4]^2-的合成及晶体结构

通过NiCl2.6H2O与双齿配体2-（二苯基膦）乙醇（Ph2PCH2CH2OH）或其氧化物2-（二苯基氧膦）乙醇[Ph2P（O）CH2CH2OH]的反应,制得两种结构新颖的阳离子型镍配合物[NiCl（Ph2PCH2CH2OH）2（H2O）]^＋Cl^-（1）和[Ni（Ph2P（O）CH2CH2OH）4]^2＋[NiCl4]^2-（2）.通过元素分析、31P核磁共振及X射线单晶衍射对配合物1和2的结构进行了表征.配合物1的晶体属单斜晶系,C2/c空间群,中心金属Ni具有六配位八面体几何构型.配合物2属四方晶系,I4（1）/a空间群,中心原子Ni与P＝＝O基团中的O配位形成平面四边形构型.     

系列异构配合物Ru(azpy)2Cl)2的结构与抗癌活性

用量子化学密度泛函(DFT)方法, 在B3LYP/LanL2DZ的水平上, 研究了一系列异构配合物α-, β-, γ-, δ-, ε-[Ru(azpy)2Cl2](azpy = 2-phenylazopyridine)(1～5)的电子结构与几何构型, 并着重研究了已报道具有优良抗癌活性的1～3的构效关系(SAR). 计算结果表明, 配合物3的两个共轭配体(azpy)的主体部分几乎处于同一平面上, 有利于插入到DNA碱基对之间. 而配合物1和2的两个共轭配体(azpy)的主体部分几乎相互垂直, 对配合物的DNA插入键合空间位阻较大. 计算结果还进一步显示了该系列异构体配合物的电子结构特征及相关性质. 作为配合物在亲电反应中起主要作用的最低未占据分子轨道(LUMO)的能量顺序为εL(2)＞εL(1)＞εL(3); 与反应活性密切相关的LUMO与最高占据分子轨道(HOMO)之间的能量差(ΔεL-H)顺序为ΔεL-H(3)＜ΔεL-H(1)＜ΔεL-H(2); 反映配合物疏水性的偶极矩顺序为µ(2)＞µ(1)＞µ(3); 此外, 与亲电反应有关的配合物共轭配体azpy上正电荷(QL)顺序为QL(3)＞QL(1)＞QL(2). 同时, 对迄今尚未见抗癌活性报道的同系列其它两个异构配合物(4和5)进行了活性预测.     

气相中CrO2^＋主活化甲烷C—H键的理论研究

用密度泛函UB3LYP／6-311＋＋G＊＊方法计算研究了气相中CrO2^＋（2^A1/4^A＂）活化甲烷C—H键的微观机理，找到了四条反应通道．对其中涉及的两态反应（TSR）进行了分析，并对影响反应机理和反应速率的势能面交叉现象（potential energy surfaces crossing）进行了详细讨论，进而运用Hammond假设和Yoshizawa等的内禀坐标单点垂直激发计算的方法找出了一系列势能面交叉点[crossing points（CPs）]，并作了相应的讨论．进一步用碎片分子轨道理论[fragment molecular orbital（FMO）]对TS1中的轨道相互作用进行了分析，解释了CrO2^＋活化甲烷C—H键的机理．     

方波伏安法研究[Ru（bpy）2dppz]2+与DNA的相互作用

合成了含有嵌入配体二吡啶并[3,2-a:2′,3′-c]-吩嗪(dppz)的钌配合物二联吡啶二吡啶并[3,2-a;2′,3′-c]吩嗪钌([Ru(bpy)2dppz]2+),并对其结构和物理化学性质进行了表征。采用方波伏安法研究了[Ru(bpy)2dppz]2+与天然双链小牛胸腺DNA的相互作用,实验结果表明,[Ru(bpy)2dppz]2+配合物的嵌入配体会嵌入DNA的碱基对中,与DNA结合形成体积较大的"金属配合物-DNA"联合体,该联合体在电解质溶液中扩散速度较慢,导致溶液中游离的钌配合物分子减少,峰电流信号降低。计算得到[Ru(bpy)2dppz]2+与DNA的结合常数Ka=1.7×105 L/mol,结合位点n=0.84。     

Spectroscopy studies on DNA binding of two ruthenium complexes [Ru(MeIm)4(L)]2+ (L = iip and tip)

Two ruthenium(II) complexes [Ru(MeIm)₄(L)]²⁺ (L?=?2-(imidazo-4-group)-1H-imidazo-[4,5-f][1,10]phenanthroline, 2-(thiophene-2-group)-1H-imidazo[4,5-f][1,10]phenanthroline, MeIm?=?1-methylimidazole) have been synthesized according to literature and structurally characterized. The interaction of the complexes with calf thymus DNA has been explored using electronic absorption titration, competitive binding experiment, circular dichroism, thermal denaturation, and viscosity measurements. The results show that both complexes could bind DNA in a intercalation mode and the DNA-binding affinity of [Ru(MeIm)₄(tip)]²⁺ (K _b?=?(7.2?±?0.3)?×?10⁵?(mol?L^?1)^?1) is greater than that of [Ru(MeIm)₄(iip)]²⁺ (K _b?=?(6.1?±?0.2)?×?10⁵?(mol?L^?1)^?1).     

亚铜配合物的光致发光与电致发光研究

亚铜[Cu（Ⅰ）]配合物因其低廉的价格、多样化的结构和独特的光物理性质一直备受关注.本文综述了常见磷光Cu（Ⅰ）配合物[Cu（NN）2]＋、[Cu（NN）（PP）]＋和（CuX）mLn（其中NN表示双齿二胺配体,PP表示二膦配体,X表示卤素,L表示含N或P配体）的光致发光与电致发光研究,揭示配合物结构与光学性质的关系,探讨近年来Cu（I）配合物在有机发光二极管（OLED）领域的应用研究新进展.     

Comparative Studies on DNA Binding,Photocleavage, and Photophysical Properties of Ru(II) Complexes Containing TIP {TIP = 2-(Thiophen-2-yl)-1H-imidazo[4,5-f][1,10]-phenanthroline} Ligand

Russian Journal of General Chemistry - A thiophene contained imidazo phenanthroline ligand TIP {TIP = 2-(thiophen-2-yl)-1H-imidazo-[4,5-f][1,10]phenanthroline{ and its mononuclear Ru(II)...     

New star-shaped trinuclear Ru(II) polypyridine complexes of imidazo[4,5-f][1,10]phenanthroline derivatives: syntheses, characterization, photophysical and electrochemical properties

A series of new star-shaped trinuclear Ru(II) complexes of imidazo[4,5-f][1,10]phenanthroline derivatives, [{Ru(bpy)(2)}(3){μ-mes(1,4-phO-Izphen)(3)}](ClO(4))(6)·4H(2)O (6), [{Ru(phen)(2)}(3){μ-mes(1,4-phO-Izphen)(3)}](ClO(4))(6)·3H(2)O (7), [{Ru(bpy)(2)}(3){μ-mes(1,2-phO-Izphen)(3)}](ClO(4))(6)·4H(2)O (8), and [{Ru(phen)(2)}(3){μ-mes(1,2-phO-Izphen)(3)}](ClO(4))(6)·3H(2)O (9) [mes(1,4-phO-Izphen)(3) (4) = 2,4,6-tri methyl-1,3,5-tris(4-oxymethyl-1-yl(1H-imidazo-2-yl-[4,5-f][1,10]phenanthroline)phenyl)benzene and (mes(1,2-phO-Izphen)(3) (5) = 2,4,6-trimethyl-1,3,5-tris(2-oxymethyl-1-yl(1H-imidazo-2-yl[4,5-f][1,10]phenanthroline)phenyl)benzene] have been synthesized and characterized. Their photophysical and electrochemical properties have also been studied. The core molecule, 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene (1) and the trialdehyde intermediate, 2,4,6-trimethyl-1,3,5-tris(4-oxymethyl-1-formylphenyl)benzene (2) are characterized by single crystal X-ray diffraction: triclinic, P1[combining macron]. The complexes 6-9 exhibit Ru(II) metal centered emission at 618, 601, 615, and 605 nm, respectively, in fluid solution at room temperature. The emission profile and emission maxima are similar and independent of the excitation wavelength for each complex. The complexes 6-9 undergo metal centered oxidation and the E(1/2) values for the Ru(II)/Ru(III) redox couples are 1.33, 1.34, 1.35, and 1.35 V versus Ag/Ag(+), respectively, which are cathodically shifted with respect to that of the mononuclear complex [Ru(bpy)(2)(PIP)](2+) (PIP = 2-phenylimidazo[4,5-f][1,10]phenanthroline). The study demonstrates the versatility of the highly symmetric trinucleating imidazo[4,5-f][1,10]phenanthroline-based core ligands 4 and 5 in forming trinuclear Ru(II) complexes.     

Synthesis,characterization, and DNA binding of ruthenium(II) complexes with 2-benzo[b] furan-2-yl-1H-imidazo[4,5f][1,10]phenanthroline as an intercalative ligand

DNA-binding properties of a number of ruthenium complexes with different polypyridine ligands are reported. The new polypyridine ligand BFIP (=2-benzo[b] furan-2-yl-1H-imidazo[4,5-f][1,10]phenanthroline) and its ruthenium complexes [Ru(bpy)₂BFIP]²⁺ (bpy = 2,2′-bipyridine), [Ru(dmb)₂BFIP]²⁺ (dmb = 4,4′-dimethyl-2,2′-bipyridine), and [Ru(phen)₂BFIP]²⁺ (phen = 1,10-phenanthroline) have been synthesized and characterized by elemental analysis, mass spectra, IR, UV-Vis, ¹H- and ¹³C-NMR, and cyclic voltammetry. The DNA binding of these complexes to calf-thymus DNA (CT-DNA) was investigated by spectrophotometric, fluorescence, and viscosity measurements. The results suggest that ruthenium(II) complexes bind to CT-DNA through intercalation. Photocleavage of pBR 322 DNA by these complexes was also studied, and [Ru(phen)₂BFIP]²⁺ was found to be a much better photocleavage agent than the other two complexes.     

Synthesis,characterization, DNA-binding and DNA-photocleavage studies of [Ru(bpy)2(BPIP)] and [Ru(phen)2(BPIP)] (BPIP = 2-(4′-biphenyl)imidazo[4,5-f][1,10]phenanthroline)

New ligand 2-(4′-biphenyl)imidazo[4,5-f][1,10]phenanthroline (BPIP) and its complexes [Ru(bpy)₂(BPIP)]²⁺ (1) (bpy = 2,2′-bipyridine) and [Ru(phen)₂(BPIP)]²⁺ (2) (phen = 1,10-phenanthroline) have been synthesized and characterized by mass spectroscopy, ¹H NMR and cyclic voltammetry. The interaction of two Ru(II) complexes with calf thymus DNA (CT-DNA) was investigated by spectroscopic and viscosity measurements. Results indicate that both complexes bind to DNA via an intercalative mode and the DNA-binding affinity of complex 2 is much greater than that of complex 1. Furthermore, when irradiated at 365 nm, both complexes have also been found to promote the photocleavage of plasmid pBR 322 DNA.     

钌配合物[Ru(bpy)2(PNT)]2+的合成、表征及与DNA相互作用研究

以cis-Ru(bpy)2Cl2·2H2O与PNT为原料合成钌(Ⅱ)多吡啶配合物[Ru(bpy)2(PNT)]2+(bpy=2,2’-联吡啶, PNT=2-[4’-(5-四唑基)苯基]咪唑-[4,5-f][1,10]邻菲咯啉), 通过元素分析、质谱和核磁共振波谱对该化合物进行了结构表征. 利用紫外-可见吸收光谱、荧光光谱、热变性和黏度实验研究了配合物与CT-DNA的相互作用, 实验结果表明, 该配合物以部分插入模式与DNA结合.     

A Ru(II) complex with 2-(4-(methylsulfonyl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline: synthesis, characterization, and acid-base and DNA-binding properties

A new Ru(II) complex of [Ru(bpy)2(Hmspip)]Cl2 {in which bpy=2,2'-bipyridine, Hmspip=2-(4-(methylsulfonyl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline} have been synthesized and characterized. The ground- and excited-state acid-base properties of [Ru(bpy)2(Hmspip)]Cl2 and its parent complex of [Ru(bpy)2(Hpip)]Cl2 {Hpip=2-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline} have been studied by UV-visible (UV-vis) and emission spectrophotometric pH titrations. [Ru(bpy)2(Hmspip)]Cl2 acts as a calf thymus DNA intercalators with a binding constant of 4.0×10(5) M(-1) in buffered 50 mM NaCl, as evidenced by UV-vis and luminescence titrations, steady-state emission quenching by [Fe(CN)6]4-, DNA competitive binding with ethidium bromide, reverse salt titrations and viscosity measurements.     

Synthesis and spectroscopic DNA binding studies of homoleptic and heteroleptic ruthenium(II) complexes with imidazo[4,5-f] [1,10]phenanthroline or its derivatives

Two series of new complexes, [Ru(phen)2L]2+ and [RuL3]2+, where phen = 1,10-phenanthroline, and L denotes imidazo[4,5-f][1,10]phenanthroline (IP) or 2-(4-R-phenyl)imidazo[4,5-f][1,10]phenanthroline(PIP, R = H; HOP, R = –OH; MOP, R = –OMe; DMNP, R = NMe2; CLP, R = Cl; NOP, R = NO2), were synthesized and characterized. Their binding to calf thymus DNA was investigated using electronic absorption and emission spectroscopy. [Ru(IP)3]2+ and each [Ru(phen)2 L]2+ showed dramatic absorption hypochromism and bathochromicity, as well as steady-state emission intensity and excited-state lifetime enhancements {except nonluminescent [Ru(phen)2NOP]2+} associated with the presence of DNA, inferring that they bind to DNA by intercalation. These phenomena were not observed for [RuL3]2+ type complexes (except L = IP), indicating that they bind to DNA at most through electrostatic interactions.